Picolinamide n-oxide compounds with fungicidal activity

ABSTRACT

This disclosure relates to picolinamide N-oxides of Formula I and their use as fungicides.

BACKGROUND & SUMMARY

Fungicides are compounds, of natural or synthetic origin, which act toprotect and/or cure plants against damage caused by agriculturallyrelevant fungi. Generally, no single fungicide is useful in allsituations. Consequently, research is ongoing to produce fungicides thatmay have better performance, are easier to use, and cost less.

The present disclosure relates to picolinamide N-oxides and their use asfungicides. The compounds of the present disclosure may offer protectionagainst ascomycetes, basidiomycetes, deuteromycetes and oomycetes.

One embodiment of the present disclosure may include compounds ofFormula I:

in which:

R₁ is hydrogen or C1-C5 alkyl, each optionally substituted with 0, 1 ormultiple R₆;

R₂ is hydrogen, C1-C5 alkyl or cycloalkyl, each optionally substitutedwith 0, 1 or multiple R₆;

R₃ is alkyl, cycloalkyl, aryl, or heteroaryl, each optionallysubstituted with 0, 1 or multiple R₆;

R₄ is hydrogen, halo, hydroxyl, alkyl, or alkoxy;

R₅ is alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy,heteroaryloxy, each optionally substituted with 0, 1 or multiple R₆;

R₆ is hydrogen, alkyl, aryl, acyl, halo, alkoxy, or heterocyclyl, eachoptionally substituted with 0, 1 or multiple R₇;

R₇ is hydrogen, alkyl, aryl, acyl, halo, alkoxy, or heterocyclyl; and

R₈ is hydrogen or C1-C5 alkyl, each optionally substituted with 0, 1 ormultiple R₆.

Another embodiment of the present disclosure may include a fungicidalcomposition for the control or prevention of fungal attack comprisingthe compounds described above and a phytologically acceptable carriermaterial.

Yet another embodiment of the present disclosure may include a methodfor the control or prevention of fungal attack on a plant, the methodincluding the steps of applying a fungicidally effective amount of oneor more of the compounds described above to at least one of the fungus,the plant, and an area adjacent to the plant.

It will be understood by those skilled in the art that the followingterms may include generic “R”-groups within their definitions, e.g.,“the term alkoxy refers to an —OR substituent”. It is also understoodthat within the definitions for the following terms, these “R” groupsare included for illustration purposes and should not be construed aslimiting or being limited by substitutions about Formula I.

The term “alkyl” refers to a branched, unbranched, or saturated cycliccarbon chain, including, but not limited to, methyl, ethyl, propyl,butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The term “alkenyl” refers to a branched, unbranched or cyclic carbonchain containing one or more double bonds including, but not limited to,ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl,cyclopentenyl, cyclohexenyl, and the like.

The term “alkynyl” refers to a branched or unbranched carbon chaincontaining one or more triple bonds including, but not limited to,propynyl, butynyl, and the like.

The terms “aryl” and “Ar” refer to any aromatic ring, mono- orbi-cyclic, containing 0 heteroatoms.

The term “heterocyclyl” refers to any aromatic or non-aromatic ring,mono- or bi-cyclic, containing one or more heteroatoms.

The term “alkoxy” refers to an —OR substituent.

The term “acyloxy” refers to an —OC(O)R substituent.

The term “cyano” refers to a —C≡N substituent.

The term “hydroxyl” refers to an —OH substituent.

The term “amino” refers to a —N(R)₂ substituent.

The term “arylalkoxy” refers to —O(CH₂)_(n)Ar where n is an integerselected from the list 1, 2, 3, 4, 5, or 6.

The term “haloalkoxy” refers to an —OR—X substituent, wherein X is Cl,F, Br, or I, or any combination thereof.

The term “haloalkyl” refers to an alkyl, which is substituted with Cl,F, I, or Br or any combination thereof.

The term “halogen” or “halo” refers to one or more halogen atoms,defined as F, Cl, Br, and I.

The term “nitro” refers to a —NO₂ substituent.

The term thioalkyl refers to an —SR substituent.

Throughout the disclosure, reference to the compounds of Formula I isread as also including all stereoisomers, for example diastereomers,enantiomers, and mixtures thereof. In another embodiment, Formula I isread as also including salts or hydrates thereof. Exemplary saltsinclude, but are not limited to: hydrochloride, hydrobromide,hydroiodide, trifluoroacetate, and trifluoromethane sulfonate.

It is also understood by those skilled in the art that additionalsubstitution is allowable, unless otherwise noted, as long as the rulesof chemical bonding and strain energy are satisfied and the productstill exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound ofFormula I, for protection of a plant against attack by a phytopathogenicorganism or the treatment of a plant infested by a phytopathogenicorganism, comprising the application of a compound of Formula I, or acomposition comprising the compound to soil, a plant, a part of a plant,foliage, and/or roots.

Additionally, another embodiment of the present disclosure is acomposition useful for protecting a plant against attack by aphytopathogenic organism and/or treatment of a plant infested by aphytopathogenic organism comprising a compound of Formula I and aphytologically acceptable carrier material.

DETAILED DESCRIPTION

The compounds of the present disclosure may be applied by any of avariety of known techniques, either as the compounds or as formulationscomprising the compounds. For example, the compounds may be applied tothe roots or foliage of plants for the control of various fungi, withoutdamaging the commercial value of the plants. The materials may beapplied in the form of any of the generally used formulation types, forexample, as solutions, dusts, wettable powders, flowable concentrate, oremulsifiable concentrates.

Preferably, the compounds of the present disclosure are applied in theform of a formulation, comprising one or more of the compounds ofFormula I with a phytologically acceptable carrier. Concentratedformulations may be dispersed in water, or other liquids, forapplication, or formulations may be dust-like or granular, which maythen be applied without further treatment. The formulations can beprepared according to procedures that are conventional in theagricultural chemical art.

The present disclosure contemplates all vehicles by which one or more ofthe compounds may be formulated for delivery and use as a fungicide.Typically, formulations are applied as aqueous suspensions or emulsions.Such suspensions or emulsions may be produced from water-soluble,water-suspendible, or emulsifiable formulations which are solids,usually known as wettable powders; or liquids, usually known asemulsifiable concentrates, aqueous suspensions, or suspensionconcentrates. As will be readily appreciated, any material to whichthese compounds may be added may be used, provided it yields the desiredutility without significant interference with the activity of thesecompounds as antifungal agents.

Wettable powders, which may be compacted to form water-dispersiblegranules, comprise an intimate mixture of one or more of the compoundsof Formula I, an inert carrier and surfactants. The concentration of thecompound in the wettable powder may be from about 10 percent to about 90percent by weight based on the total weight of the wettable powder, morepreferably about 25 weight percent to about 75 weight percent. In thepreparation of wettable powder formulations, the compounds may becompounded with any finely divided solid, such as prophyllite, talc,chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein,gluten, montmorillonite clays, diatomaceous earths, purified silicatesor the like. In such operations, the finely divided carrier andsurfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise aconvenient concentration, such as from about 1 weight percent to about50 weight percent of the compound, in a suitable liquid, based on thetotal weight of the concentrate. The compounds may be dissolved in aninert carrier, which is either a water-miscible solvent or a mixture ofwater-immiscible organic solvents, and emulsifiers. The concentrates maybe diluted with water and oil to form spray mixtures in the form ofoil-in-water emulsions. Useful organic solvents include aromatics,especially the high-boiling naphthalenic and olefinic portions ofpetroleum such as heavy aromatic naphtha. Other organic solvents mayalso be used, for example, terpenic solvents, including rosinderivatives, aliphatic ketones, such as cyclohexanone, and complexalcohols, such as 2-ethoxyethanol.

Emulsifiers which may be advantageously employed herein may be readilydetermined by those skilled in the art and include various nonionic,anionic, cationic and amphoteric emulsifiers, or a blend of two or moreemulsifiers. Examples of nonionic emulsifiers useful in preparing theemulsifiable concentrates include the polyalkylene glycol ethers andcondensation products of alkyl and aryl phenols, aliphatic alcohols,aliphatic amines or fatty acids with ethylene oxide, propylene oxidessuch as the ethoxylated alkyl phenols and carboxylic esters solubilizedwith the polyol or polyoxyalkylene. Cationic emulsifiers includequaternary ammonium compounds and fatty amine salts. Anionic emulsifiersinclude the oil-soluble salts (e.g., calcium) of alkylaryl sulfonicacids, oil-soluble salts or sulfated polyglycol ethers and appropriatesalts of phosphated polyglycol ether.

Representative organic liquids which may be employed in preparing theemulsifiable concentrates of the compounds of the present disclosure arethe aromatic liquids such as xylene, propyl benzene fractions; or mixednaphthalene fractions, mineral oils, substituted aromatic organicliquids such as dioctyl phthalate; kerosene; dialkyl amides of variousfatty acids, particularly the dimethyl amides of fatty glycols andglycol derivatives such as the n-butyl ether, ethyl ether or methylether of diethylene glycol, the methyl ether of triethylene glycol,petroleum fractions or hydrocarbons such as mineral oil, aromaticsolvents, paraffinic oils, and the like; vegetable oils such as soybeanoil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconutoil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil,safflower oil, sesame oil, tung oil and the like; esters of the abovevegetable oils; and the like. Mixtures of two or more organic liquidsmay also be employed in the preparation of the emulsifiable concentrate.Organic liquids include xylene, and propyl benzene fractions, withxylene being most preferred in some cases. Surface-active dispersingagents are typically employed in liquid formulations and in an amount offrom 0.1 to 20 percent by weight based on the combined weight of thedispersing agent with one or more of the compounds. The formulations canalso contain other compatible additives, for example, plant growthregulators and other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insolublecompounds of Formula I, dispersed in an aqueous vehicle at aconcentration in the range from about 1 to about 50 weight percent,based on the total weight of the aqueous suspension. Suspensions areprepared by finely grinding one or more of the compounds, and vigorouslymixing the ground material into a vehicle comprised of water andsurfactants chosen from the same types discussed above. Othercomponents, such as inorganic salts and synthetic or natural gums, mayalso be added to increase the density and viscosity of the aqueousvehicle.

The compounds of Formula I can also be applied as granular formulations,which are particularly useful for applications to the soil. Granularformulations generally contain from about 0.5 to about 10 weightpercent, based on the total weight of the granular formulation of thecompound(s), dispersed in an inert carrier which consists entirely or inlarge part of coarsely divided inert material such as attapulgite,bentonite, diatomite, clay or a similar inexpensive substance. Suchformulations are usually prepared by dissolving the compounds in asuitable solvent and applying it to a granular carrier which has beenpreformed to the appropriate particle size, in the range of from about0.5 to about 3 mm. A suitable solvent is a solvent in which the compoundis substantially or completely soluble. Such formulations may also beprepared by making a dough or paste of the carrier and the compound andsolvent, and crushing and drying to obtain the desired granularparticle.

Dusts containing the compounds of Formula I may be prepared byintimately mixing one or more of the compounds in powdered form with asuitable dusty agricultural carrier, such as, for example, kaolin clay,ground volcanic rock, and the like. Dusts can suitably contain fromabout 1 to about 10 weight percent of the compounds, based on the totalweight of the dust.

The formulations may additionally contain adjuvant surfactants toenhance deposition, wetting, and penetration of the compounds onto thetarget crop and organism. These adjuvant surfactants may optionally beemployed as a component of the formulation or as a tank mix. The amountof adjuvant surfactant will typically vary from 0.01 to 1.0 percent byvolume, based on a spray-volume of water, preferably 0.05 to 0.5 volumepercent. Suitable adjuvant surfactants include, but are not limited toethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols,salts of the esters or sulfosuccinic acids, ethoxylated organosilicones,ethoxylated fatty amines, blends of surfactants with mineral orvegetable oils, crop oil concentrate (mineral oil (85%)+emulsifiers(15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternaryammonium salt; blend of petroleum hydrocarbon, alkyl esters, organicacid, and anionic surfactant; C₉-C₁₁ alkylpolyglycoside; phosphatedalcohol ethoxylate; natural primary alcohol (C₁₂-C₁₆) ethoxylate;di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap;nonylphenol ethoxylate+urea ammonium nitrrate; emulsified methylatedseed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amineethoxylate (15 EO); PEG(400) dioleate-99. The formulations may alsoinclude oil-in-water emulsions such as those disclosed in U.S. patentapplication Ser. No. 11/495,228, the disclosure of which is expresslyincorporated by reference herein.

The formulations may optionally include combinations that contain otherpesticidal compounds. Such additional pesticidal compounds may befungicides, insecticides, herbicides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present disclosure in the mediumselected for application, and not antagonistic to the activity of thepresent compounds. Accordingly, in such embodiments, the otherpesticidal compound is employed as a supplemental toxicant for the sameor for a different pesticidal use. The compounds of Formula I and thepesticidal compound in the combination can generally be present in aweight ratio of from 1:100 to100:1.

The compounds of the present disclosure may also be combined with otherfungicides to form fungicidal mixtures and synergistic mixtures thereof.The fungicidal compounds of the present disclosure are often applied inconjunction with one or more other fungicides to control a wider varietyof undesirable diseases. When used in conjunction with otherfungicide(s), the presently claimed compounds may be formulated with theother fungicide(s), tank-mixed with the other fungicide(s) or appliedsequentially with the other fungicide(s). Such other fungicides mayinclude 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol,8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin,Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis,Bacillus subtilis strain QST713, benalaxyl, benomyl,benthiavalicarb-isopropyl, benzovindiflupyr,benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl,bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeauxmixture, boscalid, bromuconazole, bupirimate, calcium polysulfide,captafol, captan, carbendazim, carboxin, carpropamid, carvone,chlazafenone, chloroneb, chlorothalonil, chlozolinate, Coniothyriumminitans, copper hydroxide, copper octanoate, copper oxychloride, coppersulfate, copper sulfate (tribasic), coumoxystrobin, cuprous oxide,cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet,debacarb, diammonium ethylenebis-(dithiocarbamate), dichlofluanid,dichlorophen, diclocymet, diclomezine, dichloran, diethofencarb,difenoconazole, difenzoquat ion, diflumetorim, dimethomorph,dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap,diphenylamine, dipymetitrone, dithianon, dodemorph, dodemorph acetate,dodine, dodine free base, edifenphos, enestrobin, enestroburin,enoxastrobin, epoxiconazole, ethaboxam, ethoxyquin, etridiazole,famoxadone, fenamidone, fenaminostrobin, fenarimol, fenbuconazole,fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin,fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin hydroxide,ferbam, ferimzone, fluazinam, fludioxonil, flufenoxystrobin, flumorph,fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole,flusilazole, flusulfamide, flutianil, flutolanil, flutriafol,fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium,fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates,GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalilsulfate, imibenconazole, iminoctadine, iminoctadine triacetate,iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone,iprobenfos, iprodione, iprovalicarb, isofetamid, isoprothiolane,isopyrazam, isotianil, kasugamycin, kasugamycin hydrochloride hydrate,kresoxim-methyl, laminarin, mancopper, mancozeb, mandestrobin,mandipropamid, maneb, mefenoxam, mepanipyrim, mepronil, meptyl-dinocap,mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl,metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium,metconazole, methasulfocarb, methyl iodide, methyl isothiocyanate,metiram, metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam,nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fattyacids), orysastrobin, oxadixyl, oxathiapiprolin, oxine-copper,oxpoconazole fumarate, oxycarboxin, pefurazoate, penconazole,pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate,penthiopyrad, phenylmercury acetate, phosphonic acid, phthalide,picarbutrazox, picoxystrobin, polyoxin B, polyoxins, polyoxorim,potassium bicarbonate, potassium hydroxyquinoline sulfate, probenazole,prochloraz, procymidone, propamocarb, propamocarb hydrochloride,propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyraziflumid, pyrazophos, pyribencarb,pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole,pyroquilon, quinoclamine, quinoxyfen, quintozene, Reynoutriasachalinensis extract, sedaxane, silthiofam, simeconazole, sodium2-phenylphenoxide, sodium bicarbonate, sodium pentachlorophenoxide,spiroxamine, sulfur, SYP-Z048, tar oils, tebuconazole, tebufloquin,tecnazene, tetraconazole, thiabendazole, thifluzamide,thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb,tolylfluanid, triadimefon, triadimenol, triazoxide, triclopyricarb,tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine,triticonazole, validamycin, valifenalate, valiphenal, vinclozolin,zineb, ziram, zoxamide, Candida oleophila, Fusarium oxysporum,Gliocladium spp., Phlebiopsis gigantea, Streptomyces griseoviridis,Trichoderma spp.,(RS)—N—(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate,1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine,4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine,azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox,bentaluron, benzamacril, benzamacril-isobutyl, benzamorf, binapacryl,bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmiumcalcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone,chloraniformethan, chlorfenazole, chlorquinox, climbazole, copperbis(3-phenylsalicylate), copper zinc chromate, cufraneb, cuprichydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram,decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol,dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin,drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf,fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole,furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin,halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos,isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam,methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride,myclozolin, N-3,5-dichlorophenyl-succinimide,N-3-nitrophenylitaconimide, natamycin,N-ethylmercurio-4-toluenesulfonanilide, nickelbis(dimethyldithiocarbamate), OCH, phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb,prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor,pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinconazole,rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor,thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid,triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, andany combinations thereof.

Additionally, the compounds described herein may be combined with otherpesticides, including insecticides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present disclosure in the mediumselected for application, and not antagonistic to the activity of thepresent compounds to form pesticidal mixtures and synergistic mixturesthereof. The fungicidal compounds of the present disclosure may beapplied in conjunction with one or more other pesticides to control awider variety of undesirable pests. When used in conjunction with otherpesticides, the presently claimed compounds may be formulated with theother pesticide(s), tank-mixed with the other pesticide(s) or appliedsequentially with the other pesticide(s). Typical insecticides include,but are not limited to: 1,2-dichloropropane, abamectin, acephate,acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile,afidopyropen, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin,allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone,alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate,amitraz, anabasine, athidathion, azadirachtin, azamethiphos,azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate,barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin,beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin,biopermethrin, bistrifluron, borax, boric acid, broflanilide,bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl,bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate,butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide,camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbontetrachloride, carbophenothion, carbosulfan, cartap, cartaphydrochloride, chlorantraniliprole, chlorbicyclen, chlordane,chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos,chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform,chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos,chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerinII, cinerins, cismethrin, clacyfos, cloethocarb, closantel,clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate,copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos,crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate,cyantraniliprole, cyclaniliprole, cyclethrin, cycloprothrin, cyfluthrin,cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT,decarbofuran, deltamethrin, demephion, demephion-O, demephion-S,demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S,demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos,diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos,dicloromezotiaz, dicresyl, dicrotophos, dicyclanil, dieldrin,diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate,dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop,dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion,disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium,DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin,emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin,EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos,ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethylformate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethyleneoxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalerate, fipronil, flometoquin,flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate,flufenerim, flufenoxuron, flufenprox, flufiprole, fluhexafon,flupyradifurone, fluvalinate, fonofos, formetanate, formetanatehydrochloride, formothion, formparanate, formparanate hydrochloride,fosmethilan, fospirate, fosthietan, furathiocarb, furethrin,gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD,heptachlor, heptafluthrin, heptenophos, heterophos, hexaflumuron, HHDN,hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid,imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan,isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb,isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolinII, jodfenphos, juvenile hormone I, juvenile hormone II, juvenilehormone III, kappa-bifenthrin, kappa-tefluthrin, kelevan, kinoprene,lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane,lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox,mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride,mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion,methiocarb, methocrotophos, methomyl, methoprene, methoxychlor,methoxyfenozide, methyl bromide, methyl isothiocyanate,methylchloroform, methylene chloride, metofluthrin, metolcarb,metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime,mipafox, mirex, molosultap, momfluorothrin, monocrotophos, monomehypo,monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene,nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron,noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos,oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl,penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin,phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor,phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos,pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite,potassium thiocyanate, pp′-DDT, prallethrin, precocene I, precocene II,precocene III, primidophos, profenofos, profluralin, promacyl,promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos,prothoate, protrifenbute, pyflubumide, pyraclofos, pyrafluprole,pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins,pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen,pyriminostrobin, pyrimitate, pyriprole, pyriproxyfen, quassia,quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin,rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silicagel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodiumthiocyanate, sophamide, spinetoram, spinosad, spiromesifen,spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep,sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb,TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane,tetrachlorvinphos, tetramethrin, tetramethylfluthrin, tetraniliprole,theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime,thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon,thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin,tioxazafen, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin,triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3,trichloronat, trifenofos, triflumezopyrim, triflumuron, trimethacarb,triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin,zolaprofos, and any combinations thereof.

Additionally, the compounds described herein may be combined withherbicides that are compatible with the compounds of the presentdisclosure in the medium selected for application, and not antagonisticto the activity of the present compounds to form pesticidal mixtures andsynergistic mixtures thereof. The fungicidal compounds of the presentdisclosure may be applied in conjunction with one or more herbicides tocontrol a wide variety of undesirable plants. When used in conjunctionwith herbicides, the presently claimed compounds may be formulated withthe herbicide(s), tank-mixed with the herbicide(s) or appliedsequentially with the herbicide(s). Typical herbicides include, but arenot limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB;2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor,acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim,allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone,amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl,amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton,atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC,beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate,bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron,bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil,bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon,butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron,butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole,calcium chlorate, calcium cyanamide, cambendichlor, carbasulam,carbetamide, carboxazole, chlorprocarb, carfentrazone, CDEA, CEPC,chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine,chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop,chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen,chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham,chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin,cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop,clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam,CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron,cyanatryn, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron,cycloxydim, cycluron, cyhalofop, cyperquat, cyprazine, cyprazole,cypromid, daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn,di-allate, dicamba, dichlobenil, dichloralurea, dichlormate,dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat,diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican,diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn,dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine,dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid,dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP,eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin,ethametsulfuron, ethidimuron, ethiolate, ethofumesate, ethoxyfen,ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam,fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone, fenquinotrione,fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate,flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop, fluazifop-P,fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet,flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin,flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoromidine,fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate,flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone,fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen,glufosinate, glufosinate-P, glyphosate, halauxifen, halosafen,halosulfuron, haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone,hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic, imazapyr,imazaquin, imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil,iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine,ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin,isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben,isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox,lactofen, lenacil, linuron, MAA, MAMA, MCPA, MCPA-thioethyl, MCPB,mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine,mesosulfuron, mesotrione, metam, metamifop, metamitron, metazachlor,metazosulfuron, metflurazon, methabenzthiazuron, methalpropalin,methazole, methiobencarb, methiozolin, methiuron, methometon,methoprotryne, methyl bromide, methyl isothiocyanate, methyldymron,metobenzuron, metobromuron, metolachlor, metosulam, metoxuron,metribuzin, metsulfuron, molinate, monalide, monisouron,monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA,naproanilide, napropamide, napropamide-M, naptalam, neburon,nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat,pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol,pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham,phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate,picloram, picolinafen, pinoxaden, piperophos, potassium arsenite,potassium azide, potassium cyanate, pretilachlor, primisulfuron,procyazine, prodiamine, profluazol, profluralin, profoxydim,proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop,propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron,propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor,pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate,pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor,pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac,pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine,quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron,saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim,siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodiumazide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone,sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA,tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim,terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn,tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin,thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb,tiafenacil, tiocarbazil, tioclorim, tolpyralate, topramezone,tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam,tribenuron, tricamba, triclopyr, tridiphane, trietazine,trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron, trifop,trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac,tritosulfuron, vernolate, and xylachlor.

Another embodiment of the present disclosure is a method for the controlor prevention of fungal attack. This method comprises applying to thesoil, plant, roots, foliage, or locus of the fungus, or to a locus inwhich the infestation is to be prevented (for example applying to cerealor grape plants), a fungicidally effective amount of one or more of thecompounds of Formula I. The compounds are suitable for treatment ofvarious plants at fungicidal levels, while exhibiting low phytotoxicity.The compounds may be useful both in a protectant and/or an eradicantfashion.

The compounds have been found to have significant fungicidal effectparticularly for agricultural use. Many of the compounds areparticularly effective for use with agricultural crops and horticulturalplants.

It will be understood by those skilled in the art that the efficacy ofthe compound for the foregoing fungi establishes the general utility ofthe compounds as fungicides.

The compounds have broad ranges of activity against fungal pathogens.Exemplary pathogens may include, but are not limited to, causing agentof wheat leaf blotch (Zymoseptoria tritici), wheat brown rust (Pucciniatriticina), wheat stripe rust (Puccinia striiformis), scab of apple(Venturia inaequalis), powdery mildew of grapevine (Uncinula necator),barley scald (Rhynchosporium secalis), blast of rice (Pyriculariaoryzae), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat(Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminis f.sp. tritici), powdery mildew of barley (Blumeria graminis f. sp.hordei), powdery mildew of cucurbits (Erysiphe cichoracearum),anthracnose of cucurbits (Colletotrichum lagenarium), leaf spot of beet(Cercospora beticola), early blight of tomato (Alternaria solani), andspot blotch of barley (Cochliobolus sativus). The exact amount of theactive material to be applied is dependent not only on the specificactive material being applied, but also on the particular actiondesired, the fungal species to be controlled, and the stage of growththereof, as well as the part of the plant or other product to becontacted with the compound. Thus, all the compounds, and formulationscontaining the same, may not be equally effective at similarconcentrations or against the same fungal species.

The compounds are effective in use with plants in a disease-inhibitingand phytologically acceptable amount. The term “disease-inhibiting andphytologically acceptable amount” refers to an amount of a compound thatkills or inhibits the plant disease for which control is desired, but isnot significantly toxic to the plant. This amount will generally be fromabout 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm beingpreferred. The exact concentration of compound required varies with thefungal disease to be controlled, the type of formulation employed, themethod of application, the particular plant species, climate conditions,and the like. A suitable application rate is typically in the range fromabout 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per squaremeter, g/m²).

Any range or desired value given herein may be extended or alteredwithout losing the effects sought, as is apparent to the skilled personfor an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemicalprocedures. Intermediates not specifically mentioned in this disclosureare either commercially available, may be made by routes disclosed inthe chemical literature, or may be readily synthesized from commercialstarting materials utilizing standard procedures.

General Schemes

The following scheme illustrates an approach to generating picolinamideN-oxide compounds of Formula I. The following description and example isprovided for illustrative purposes and should not be construed aslimiting in terms of substituents or substitution patterns.

Compounds of Formula I wherein R₁, R₂, R₃, R₄, R₅, and R₈ are asoriginally defined, can be prepared according to the method outlined inScheme 1, step a. Compounds of Formula 1.0 wherein R₁, R₂, R₃, R₄, R₅,and R₈ are as originally defined, can be prepared as described by theprocedures outlined in US patent applications WO 2016/109289, WO2016/109257, and WO 2016/109302. Compounds of Formula 1.0 can be treatedwith an oxidizing reagent such as m-chloroperbenzoic acid (mCPBA) in apolar solvent such as dichloromethane (CH₂Cl₂), at a temperature ofabout 0° C. to 50° C. to afford compounds of Formula I, wherein R₁, R₂,R₃, R₄, R₅, and R₈ are as originally defined, as shown in a. It will beunderstood by those skilled in the art that compounds such as Formula Imay also be prepared using other oxidizing agents including, but notlimited to: hydrogen peroxide, hydrogen peroxide-urea complex, magnesiummonoperoxyphthalate hexahydrate (MMPP), peroxyacetic acid, oxone, sodiumperchlorate or dimethyl dioxirane.

EXAMPLES Example 1 Preparation of2-(((S)-1-(((S)-1,1-bis(2,4-dimethylphenyl)propan-2-yl)oxy)-1-oxopropan-2-yl)carbamoyl)-3-hydroxy-4-methoxypyridine1-oxide. Compound 1

To a solution of (S)-1,1-bis(2,4-dimethylphenyl)propan-2-yl(3-hydroxy-4-methoxypicolinoyl)-L-alaninate (WO 2016/109257) (0.025 g,0.051 mmol) in CH₂Cl₂ (0.51 mL) was added m-chloroperbenzoic acid (≦70%,0.025 g, 0.102 mmol). The mixture was stirred at room temperatureovernight. The mixture was concentrated under reduced pressure and thecrude residue was purified via flash chromatography (4 g silica column)using a 0-45% acetone/hexanes mixture as the eluent to provide the titlecompound (21 mg, 80% yield) as a white foam. ¹H NMR (500 MHz, CDCl₃) δ14.31 (s, 1H), 12.64 (d, J=7.0 Hz, 1H), 7.85 (d, J=7.2 Hz, 1H), 7.17 (d,J=7.9 Hz, 1H), 7.11 (d, J=7.7 Hz, 1H), 6.98 −6.88 (m, 3H), 6.80 (s, 1H),6.75 (d, J=7.1 Hz, 1H), 5.67 (dq, J=10.2, 6.1 Hz, 1H), 4.52 −4.38 (m,2H), 3.96 (s, 3H), 2.35 (s, 3H), 2.28 (s, 3H), 2.24 (s, 3H), 2.20 (s,3H), 1.30 (d, J=6.2 Hz, 3H), 1.11 (d, J=7.2 Hz, 3H). IR (thin film)2934, 1736, 1644, 1569, 1533, 1480, 1454, 1301, 1207, 1155, 1030, 911,808, 733 cm⁻¹. ESIMS m/z 507.2 [(M+H)+].

Compound structures, appearance, and preparation methods of compound ofthe present disclosure are shown below in Table 1. Analytical data forcompounds shown in Table 1 is shown below in Table 2.

Example A Evaluation of Fungicidal Activity: Leaf Blotch of Wheat(Zymoseptoria tritici; Bayer Code SEPTTR)

Technical grades of materials were dissolved in acetone, which were thenmixed with nine volumes of water (H₂O) containing 110 ppm Triton X-100.The fungicide solutions were applied onto wheat seedlings using anautomated booth sprayer to run-off. All sprayed plants were allowed toair dry prior to further handling. All fungicides were evaluated usingthe aforementioned method for their activity vs. all target diseases,unless stated otherwise. Wheat leaf blotch and brown rust activity werealso evaluated using track spray applications, in which case thefungicides were formulated as EC formulations, containing 0.1% Trycol5941 in the spray solutions.

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Zymoseptoria tritici either prior to orafter fungicide treatments. After inoculation the plants were kept in100% relative humidity (one day in a dark dew chamber followed by two tothree days in a lighted dew chamber at 20° C.) to permit spores togerminate and infect the leaf. The plants were then transferred to agreenhouse set at 20° C. for disease to develop. When disease symptomswere fully expressed on the 1^(st) leaves of untreated plants, infectionlevels were assessed on a scale of 0 to 100 percent disease severity.Percent disease control was calculated using the ratio of diseaseseverity on treated plants relative to untreated plants. Results of theevaluations are shown below in Table 4.

Example B Evaluation of Fungicidal Activity: Wheat Brown Rust (PucciniatriticinaSynonym: Puccinia recondita f. sp. tritici; Bayer Code PUCCRT)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Puccinia triticina either prior to orafter fungicide treatments. After inoculation the plants were kept in adark dew room at 22° C. with 100% relative humidity overnight to permitspores to germinate and infect the leaf. The plants were thentransferred to a greenhouse set at 24° C. for disease to develop.Fungicide formulation, application and disease assessment followed theprocedures as described in the Example A. Results of the evaluations areshown below in Table 4.

Example C Evaluation of Fungicidal Activity: Asian Soybean Rust(Phakopsora pachyrhizi; Bayer Code PHAKPA)

Technical grades of materials were dissolved in acetone, which were thenmixed with nine volumes of H₂O containing 0.011% Tween 20. The fungicidesolutions were applied onto soybean seedlings using an automated boothsprayer to run-off. All sprayed plants were allowed to air dry prior tofurther handling.

Soybean plants (variety Williams 82) were grown in soil-less Metro mix,with one plant per pot. Two weeks old seedlings were used for testing.Plants were inoculated either 3 days prior to or 1 day after fungicidetreatments. Plants were incubated for 24 h in a dark dew room at 22° C.and 100% relative humidity then transferred to a growth room at 23° C.for disease to develop. Disease severity was assessed on the sprayedleaves. Results of the evaluations are shown below in Table 5.

TABLE 1 Compound Structure, Preparation Method, and Appearance AsPrepared Cmpd. According No. Structure To Appearance  1

WO 2016/109257 Example 1 White Foam  2

WO 2016/109257 Example 1 White Foam  3

WO 2016/109257 Example 1 White Foam  4

WO 2016/109257 Example 1 White Foam  5

WO 2016/109257 Example 1 White Foam  6

WO 2016/109257 Example 1 White Foam  7

WO 2016/109257 Example 1 White Foam  8

WO 2016/109289 Example 1 Thick Oil  9

WO 2016/109257 Example 1 White Foam 10

WO 2016/109302 Example 1 Thick Oil 11

WO 2016/109257 Example 1 White Foam 12

WO 2016/109257 Example 1 White Foam 13

WO 2016/109257 Example 1 Glassy White Solid 14

WO 2016/109257 Example 1 Yellow Semisolid 15

WO 2016/109257 Example 1 White Semisolid 16

WO 2016/109257 Example 1 Yellow/Orange Semisolid 17

WO 2016/109257 Example 1 White Semisolid 18

WO 2016/109257 Example 1 Yellow Semisolid 19

WO 2016/109257 Example 1 Clear, Colorless Oil 20

WO 2016/109257 Example 1 Pale Yellow Semisolid 21

WO 2016/109257 Example 1 White Semisolid 22

WO 2016/109257 Example 1 Colorless Oil 23

WO 2016/109257 Example 1 Colorless Oil 24

WO 2016/109257 Example 1 Colorless Oil 25

WO 2016/109257 Example 1 Colorless Oil 26

WO 2016/109257 Example 1 White Wax 27

WO 2016/109257 Example 1 Colorless Oil 28

WO 2016/109257 Example 1 White Wax 29

WO 2016/109257 Example 1 Colorless Oil 30

WO 2016/109257 Example 1 Colorless Oil 31

WO 2016/109257 Example 1 Colorless Oil 32

WO 2016/109257 Example 1 Thick Oil 33

WO 2016/109257 Example 1 White Foam 34

WO 2016/109257 Example 1 White Foam 35

WO 2016/109257 Example 1 White Foam 36

WO 2016/109257 Example 1 White Foam 37

WO 2016/109257 Example 1 White Foam 38

WO 2016/109257 Example 1 White Foam 39

WO 2016/109257 Example 1 White Foam 40

WO 2016/109257 Example 1 Thick Oil 41

WO 2016/109257 Example 1 Thick Oil *Cmpd. No.—Compound Number

TABLE 2 Analytical Data Cmpd. No. IR (cm⁻¹) MASS SPEC NMR 1 IR (thinESIMS m/z 507.2 ¹H NMR (500 MHz, CDCl₃) δ 14.31 (s, film) 2934, ([M +H]⁺) 1H), 12.64 (d, J = 7.0 Hz, 1H), 7.85 (d, J = 1736, 1644, 7.2 Hz,1H), 7.17 (d, J = 7.9 Hz, 1H), 1569, 1533, 7.11 (d, J = 7.7 Hz, 1H),6.98-6.88 (m, 1480, 1454, 3H), 6.80 (s, 1H), 6.75 (d, J = 7.1 Hz, 1301,1207, 1H), 5.67 (dq, J = 10.2, 6.1 Hz, 1H), 1155, 1030, 4.52-4.38 (m,2H), 3.96 (s, 3H), 2.35 911, 808, (s, 3H), 2.28 (s, 3H), 2.24 (s, 3H),2.20 733 cm⁻¹ (s, 3H), 1.30 (d, J = 6.2 Hz, 3H), 1.11 (d, J = 7.2 Hz,3H). 2 IR (thin ESIMS m/z 469.1 ¹H NMR (500 MHz, CDCl₃) δ 14.26 (s,film) 2981, ([M + H]⁺) 1H), 12.64 (d, J = 7.1 Hz, 1H), 7.85 (d, J =1737, 1644, 7.2 Hz, 1H), 7.29-7.18 (m, 6H), 7.16- 1605, 1570, 7.08 (m,1H), 6.96 (t, J = 8.7 Hz, 2H), 1534, 1509, 6.76 (d, J = 7.1 Hz, 1H),5.76 (dq, J = 1479, 1424, 10.0, 6.2 Hz, 1H), 4.48 (p, J = 7.2 Hz, 1301,1220, 1H), 4.05 (d, J = 10.0 Hz, 1H), 3.97 (s, 1156, 911, 3H), 1.25 (d,J = 6.2 Hz, 3H), 1.05 (d, J = 812, 733 7.2 Hz, 3H). cm⁻¹ 3 IR (thinESIMS m/z 547.1 ¹H NMR (500 MHz, CDCl₃) δ 14.28 (s, film) 2938, ([M +H]⁺) 1H), 12.66 (d, J = 7.1 Hz, 1H), 7.85 (d, J = 1738, 1623, 7.2 Hz,1H), 7.31-7.23 (m, 1H), 7.16 1570, 1533, (t, J = 8.5 Hz, 1H), 6.75 (d, J= 7.2 Hz, 1506, 1480, 1H), 6.64-6.54 (m, 3H), 6.47 (dd, J = 1456, 1299,12.1, 2.6 Hz, 1H), 5.77 (dq, J = 12.2, 6.2 1154, 1030, Hz, 1H), 4.62 (d,J = 10.3 Hz, 1H), 4.54 911, 734 (p, J = 7.2 Hz, 1H), 3.97 (s, 3H), 3.75(s, cm⁻¹ 3H), 3.73 (s, 3H), 1.28 (d, J = 6.1 Hz, 3H), 1.18 (d, J = 7.3Hz, 3H). 4 IR (thin ESIMS m/z 547.1 ¹H NMR (500 MHz, CDCl₃) δ 14.26 (s,film) 2938, ([M + H]⁺) 1H), 12.67 (d, J = 7.1 Hz, 1H), 7.85 (d, J =1739, 1644, 7.2 Hz, 1H), 6.98-6.90 (m, 2H), 6.88- 1570, 1534, 6.79 (m,2H), 6.76 (d, J = 7.2 Hz, 1H), 1497, 1424, 6.70 (dt, J = 9.0, 3.5 Hz,1H), 6.65- 1208, 1153, 6.59 (m, 1H), 5.84 (dq, J = 12.0, 6.1 Hz, 1032,911, 1H), 4.69 (d, J = 10.4 Hz, 1H), 4.53 (p, J = 809, 732 7.2 Hz, 1H),3.97 (s, 3H), 3.74 (s, 6H), cm⁻¹ 1.31 (d, J = 6.1 Hz, 3H), 1.15 (d, J =7.2 Hz, 3H). 5 IR (thin ESIMS m/z 588.9 ¹H NMR (500 MHz, CDCl₃) δ 14.15(s, film) 2937, ([M + H]⁺) 1H), 12.70 (d, J = 7.0 Hz, 1H), 7.85 (d, J =1739, 1643, 7.2 Hz, 1H), 7.42-7.28 (m, 4H), 7.10 1570, 1533, (dd, J =8.4, 2.2 Hz, 1H), 7.06 (dd, J = 1473, 1424, 8.4, 2.1 Hz, 1H), 6.77 (d, J= 7.2 Hz, 1302, 1205, 1H), 5.64 (dq, J = 9.6, 6.2 Hz, 1H), 4.53 1154,1133, (p, J = 7.2 Hz, 1H), 4.00 (d, J = 9.5 Hz, 1029, 910, 1H), 3.97 (s,3H), 1.27-1.20 (m, 6H). 732 cm⁻¹ 6 IR (thin ESIMS m/z 555.0 ¹H NMR (500MHz, CDCl₃) δ 14.14 (s, film) 2939, ([M + H]⁺) 1H), 12.71 (d, J = 7.0Hz, 1H), 7.86 (d, J = 1739, 1644, 7.2 Hz, 1H), 7.35-7.27 (m, 2H), 7.07-1572, 1533, 6.93 (m, 4H), 6.77 (d, J = 7.2 Hz, 1H), 1484, 1424, 5.65(dq, J = 9.4, 6.1 Hz, 1H), 4.53 (p, J = 1301, 1244, 7.1 Hz, 1H), 4.03(d, J = 9.4 Hz, 1H), 1205, 1155, 3.97 (s, 3H), 1.26 (d, J = 6.2 Hz, 3H),1062, 910, 1.24 (d, J = 7.2 Hz, 3H). 733 cm⁻¹ 7 IR (thin ESIMS m/z 547.0¹H NMR (500 MHz, CDCl₃) δ 14.23 (d, film) 2981, ([M + H]⁺) J = 0.5 Hz,1H), 12.65 (d, J = 7.0 Hz, 1737, 1643, 1H), 7.84 (d, J = 7.2 Hz, 1H),7.24 (d, J = 1570, 1533, 8.2 Hz, 1H), 7.16 (d, J = 8.2 Hz, 1H), 1479,1424, 7.08 (dd, J = 7.5, 2.2 Hz, 2H), 7.06- 1301, 1205, 6.96 (m, 2H),6.76 (d, J = 7.2 Hz, 1H), 1154, 1047, 5.69 (dq, J = 9.9, 6.1 Hz, 1H),4.50 (p, J = 910, 732 7.2 Hz, 1H), 3.97 (s, 3H), 3.95 (d, J = cm⁻¹ 10.1Hz, 1H), 2.32 (s, 3H), 2.28 (s, 3H), 1.24 (d, J = 6.1 Hz, 3H), 1.14 (d,J = 7.3 Hz, 3H). 8 IR (thin ESIMS m/z 447.1 ¹H NMR (500 MHz, CDCl₃) δ14.32 (s, film) 2968, ([M + H]⁺) 1H), 12.74 (d, J = 7.1 Hz, 1H), 7.85(d, J = 1739, 1645, 7.2 Hz, 1H), 7.20 (dd, J = 8.7, 7.3 Hz, 1595, 1570,2H), 6.93-6.83 (m, 3H), 6.75 (d, J = 1539, 1488, 7.2 Hz, 1H), 5.11 (dt,J = 9.4, 3.8 Hz, 1303, 1239, 1H), 4.56 (p, J = 7.1 Hz, 1H), 4.24 (dd, J= 1205, 1157, 6.7, 4.4 Hz, 1H), 3.96 (s, 3H), 1.98 (dt, 910, 756, J =13.5, 6.8 Hz, 1H), 1.88-1.71 (m, 736 cm⁻¹ 2H), 1.28 (d, J = 7.2 Hz, 3H),1.03 (d, J = 6.7 Hz, 3H), 1.01 (d, J = 6.9 Hz, 3H), 0.93 (t, J = 7.4 Hz,3H). 9 IR (thin ESIMS m/z 571.0 ¹H NMR (500 MHz, CDCl₃) δ 13.63 (s,film) 1742, ([M + H]⁺) 1H), 12.49 (d, J = 9.2 Hz, 1H), 7.83 (d, J =1654, 1575, 7.2 Hz, 1H), 7.32-7.26 (m, 2H), 7.17 1484, 1422, (dd, J =8.4, 7.6 Hz, 1H), 7.04-6.97 (m, 1304, 1242, 2H), 6.93 (dd, J = 8.4, 2.2Hz, 1H), 6.76 1157, 1059, (d, J = 7.2 Hz, 1H), 5.69 (q, J = 6.3 Hz, 911,734 1H), 4.91 (s, 1H), 4.76 (dq, J = 9.3, 7.3 cm⁻¹ Hz, 1H), 4.00 (s,3H), 1.48 (d, J = 7.3 Hz, 3H), 1.17 (d, J = 6.2 Hz, 3H). 10 IR (thinESIMS m/z 433.1 ¹H NMR (500 MHz, CDCl₃) δ 14.38 (d, film) 2965, ([M +H]⁺) J = 0.5 Hz, 1H), 12.85 (d, J = 6.9 Hz, 1744, 1644, 1H), 7.87 (d, J= 7.2 Hz, 1H), 7.29- 1570, 1532, 7.23 (m, 2H), 6.98-6.91 (m, 1H), 6.871481, 1424, (dt, J = 7.9, 1.0 Hz, 2H), 6.77 (d, J = 7.2 1302, 1240, Hz,1H), 5.07 (dd, J = 6.3, 5.3 Hz, 1H), 1203, 1154, 4.76 (p, J = 7.2 Hz,1H), 4.51 (p, J = 6.1 1028, 944, Hz, 1H), 3.97 (s, 3H), 2.19-2.09 (m,911, 755, 1H), 1.63 (d, J = 7.2 Hz, 3H), 1.31 (d, J = 736 cm⁻¹ 6.2 Hz,3H), 0.97 (d, J = 6.9 Hz, 3H), 0.91 (d, J = 6.7 Hz, 3H). 11 IR (thinESIMS m/z 604.9 ¹H NMR (500 MHz, CDCl₃) δ 13.60 (s, film) 2986, ([M +H]⁺) 1H), 12.47 (d, J = 9.2 Hz, 1H), 7.81 (d, J = 1741, 1645, 7.1 Hz,1H), 7.55 (d, J = 2.1 Hz, 1H), 1574, 1465, 7.33 (d, J = 8.5 Hz, 1H),7.29 (d, J = 2.2 1304, 1251, Hz, 1H), 7.21 (d, J = 8.3 Hz, 1H), 7.101158, 1028, (dd, J = 8.4, 2.1 Hz, 1H), 7.01 (dd, J = 910, 813, 8.5, 2.2Hz, 1H), 6.77 (d, J = 7.2 Hz, 732 cm⁻¹ 1H), 5.67 (q, J = 6.2 Hz, 1H),4.97 (s, 1H), 4.78 (dq, J = 9.3, 7.3 Hz, 1H), 4.00 (s, 3H), 1.49 (d, J =7.3 Hz, 3H), 1.17 (d, J = 6.2 Hz, 3H). 12 IR (thin ESIMS m/z 583.1 ¹HNMR (500 MHz, CDCl₃) δ 14.21 (s, film) 2941, ([M + H]⁺) 1H), 12.66 (d, J= 7.0 Hz, 1H), 7.83 (d, J = 1737, 1644, 7.2 Hz, 1H), 7.06 (ddd, J = 8.3,5.3, 1570, 1535, 2.1 Hz, 1H), 6.87-6.71 (m, 4H), 5.65 1500, 1475, (dq, J= 8.4, 6.2 Hz, 1H), 4.85 (d, J = 9.8 1428, 1294, Hz, 1H), 4.58-4.48 (m,1H), 4.00- 1027, 1154, 3.95 (m, 6H), 3.84 (d, J = 2.0 Hz, 3H), 1057,950, 1.25 (d, J = 5.3 Hz, 3H), 1.24 (d, J = 4.2 911, 808, Hz, 3H). 732cm⁻¹ 13 IR (thin ESIMS m/z 487.1 ¹H NMR (500 MHz, CDCl₃) δ 14.22 (s,film) 2983, ([M + H]⁺) 1H), 12.65 (d, J = 7.0 Hz, 1H), 7.85 (d, J =1737, 1643, 7.1 Hz, 1H), 7.26-7.16 (m, 4H), 6.97 1570, 1507, (t, J = 8.7Hz, 2H), 6.91 (t, J = 8.7 Hz, 1479, 1453, 2H), 6.76 (d, J = 7.2 Hz, 1H),5.70 (dq, J = 1301, 1221, 9.8, 6.1 Hz, 1H), 4.50 (p, J = 7.1 Hz, 1157,1137, 1H), 4.05 (d, J = 9.8 Hz, 1H), 3.97 (s, 1029, 908, 3H), 1.24 (d, J= 6.2 Hz, 3H), 1.14 (d, J = 824, 729, 7.2 Hz, 3H). 673 cm⁻¹ ¹³C NMR (126MHz, CDCl₃) δ 170.97, 165.41, 162.70, 162.53, 160.74, 160.57, 152.49,149.36, 136.93, 136.90, 136.80, 136.77, 130.86, 129.53, 129.50, 129.47,129.44, 123.60, 115.78, 115.61, 115.37, 115.20, 107.63, 73.21, 56.53,56.09, 48.66, 19.04, 17.14. 14 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz,CDCl₃) δ 14.30 (s, film) 2936, [M + H]⁺ calcd 1H), 12.62 (d, J = 7.2 Hz,1H), 7.85 (d, J = 1738, 1595, for C₂₉H₃₅N₂O₈, 7.0 Hz, 1H), 6.75 (d, J =7.2 Hz, 1H), 1573, 1481, 539.2388; found, 6.72-6.57 (m, 5H), 6.57-6.40(m, 1296, 1154, 539.2409 2H), 5.79-5.68 (m, 1H), 4.49 (t, J = 7.1 1067,736 Hz, 1H), 3.96 (s, 3H), 3.75 (s, 3H), 3.72 cm⁻¹ (s, 3H), 2.28 (s,3H), 2.23 (s, 3H), 1.36- 1.18 (m, 3H), 1.07 (d, J = 7.2 Hz, 3H). 15 IR(thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 14.32 (s, film) 2937,[M + H]⁺ calcd 1H), 12.60 (d, J = 7.1 Hz, 1H), 7.91- 1737, 1571, forC₂₉H₃₅N₂O₆, 7.81 (m, 1H), 7.01 (q, J = 4.8, 4.1 Hz, 1481, 1302,507.2490; found, 5H), 6.93 (d, J = 8.2 Hz, 1H), 6.75 (d, J = 1209, 1029,507.2519 7.3 Hz, 1H), 5.75 (dq, J = 10.2, 6.1 733 cm⁻¹ Hz, 1H), 4.48 (p,J = 7.1 Hz, 1H), 3.96 (s, 3H), 3.91 (d, J = 10.4 Hz, 1H), 2.20 (s, 3H),2.17 (s, 3H), 2.15 (s, 3H), 2.13 (s, 3H), 1.24 (d, J = 6.1 Hz, 3H), 1.05(d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 171.08, 165.31, 152.56,149.28, 139.27, 139.09, 136.80, 136.33, 134.95, 134.50, 130.87, 129.91,129.54, 129.36, 129.24, 125.32, 125.07, 123.79, 107.61, 73.64, 57.13,56.50, 48.64, 19.86, 19.76, 19.28, 19.24, 19.20, 17.15. 16 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 14.34 (s, film) 2942, [M + H]⁺calcd 1H), 12.59 (d, J = 7.1 Hz, 1H), 7.85 (dd, 1738, 1499, forC₂₉H₃₅N₂O₁₀, J = 7.2, 3.2 Hz, 1H), 7.04 (d, J = 3.0 Hz, 1224, 1048,571.2286; found, 1H), 6.89 (s, 1H), 6.81-6.72 (m, 2H), 735 cm⁻¹ 571.23226.71-6.64 (m, 2H), 6.61 (dd, J = 8.8, 3.0 Hz, 1H), 5.94 (dq, J = 10.3,6.1 Hz, 1H), 4.91 (d, J = 10.1 Hz, 1H), 4.50 (p, J = 7.0 Hz, 1H), 3.96(d, J = 3.4 Hz, 3H), 3.81 (s, 3H), 3.73 (s, 3H), 3.71 (s, 6H), 1.25 (d,J = 6.7 Hz, 3H), 1.09 (d, J = 7.2 Hz, 3H). 17 IR (thin HRMS-ESI (m/z) ¹HNMR (400 MHz, CDCl₃) δ 14.25 (s, film) 2933, [M + H]⁺ calcd 1H), 12.63(d, J = 7.0 Hz, 1H), 7.86 (d, J = 1737, 1533, for C₂₇H₂₉F₂N₂O₆, 7.1 Hz,1H), 7.04 (td, J = 6.9, 3.7 Hz, 1501, 1239, 515.1988; found, 4H), 6.90(dd, J = 10.2, 7.8 Hz, 1H), 1118, 731 515.2023 6.87-6.80 (m, 1H), 6.76(d, J = 7.2 Hz, cm⁻¹ 1H), 5.67 (dq, J = 10.0, 6.0 Hz, 1H), 4.49 (p, J =7.2 Hz, 1H), 3.97 (s, 3H), 3.94 (d, J = 10.4 Hz, 1H), 2.23 (d, J = 1.9Hz, 3H), 2.20-2.17 (m, 3H), 1.23 (d, J = 6.1 Hz, 3H), 1.12 (d, J = 7.2Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −119.99, −120.53. 18 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 14.28 (s, film) 2935, [M + H]⁺calcd 1H), 12.61 (d, J = 7.1 Hz, 1H), 7.85 (d, J = 1736, 1572, forC₂₉H₃₅N₂O₈, 7.2 Hz, 1H), 7.02 (d, J = 7.7 Hz, 1H), 1455, 1208, 539.2388;found, 6.94 (d, J = 7.6 Hz, 1H), 6.81-6.66 (m, 1154, 1137, 539.2419 6H),5.79 (dq, J = 12.3, 6.1 Hz, 1H), 1035, 732 4.49 (p, J = 7.1 Hz, 1H),3.96 (s, 3H), cm⁻¹ 3.79 (s, 3H), 3.77 (s, 3H), 2.13 (s, 3H), 2.09 (s,3H), 1.26 (t, J = 3.1 Hz, 3H), 1.07 (d, J = 7.2 Hz, 3H). ¹³C NMR (101MHz, CDCl₃) δ 171.14, 165.33, 157.85, 157.61, 152.56, 149.31, 140.43,140.23, 130.83, 130.75, 130.42, 125.21, 124.75, 119.76, 119.54, 109.77,109.73, 107.62, 73.39, 57.91, 56.50, 55.29, 55.25, 48.69, 29.30, 19.22,17.16, 15.80, 15.70. 19 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃)δ 14.23 (s, film) 2933, [M + H]⁺ calcd 1H), 12.65 (d, J = 7.1 Hz, 1H),7.87 (d, J = 1737, 1571, for C₂₇H₂₉F₂N₂O₆, 7.2 Hz, 1H), 7.06 (dt, J =21.0, 7.9 Hz, 1506, 1423, 515.1988; found, 2H), 6.99-6.83 (m, 5H), 6.77(d, J = 1206, 1155, 515.1983 7.1 Hz, 1H), 5.68 (dq, J = 9.9, 6.1 Hz, 733cm⁻¹ 1H), 4.51 (p, J = 7.2 Hz, 1H), 3.97 (s, 3H), 2.20 (d, J = 1.8 Hz,3H), 2.16 (d, J = 1.8 Hz, 3H), 1.24 (d, J = 6.1 Hz, 3H), 1.16 (d, J =7.2 Hz, 3H). ¹⁹F NMR (376 MHz, CDCl₃) δ −116.62, −117.26. 20 IR (thinHRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 14.32 (s, film) 2935, [M + H]⁺calcd 1H), 12.62 (d, J = 7.2 Hz, 1H), 7.85 (d, J = 1737, 1571, forC₂₉H₃₅N₂O₈, 7.1 Hz, 1H), 7.10-6.98 (m, 4H), 6.79- 1504, 1247, 539.2388;found, 6.64 (m, 3H), 5.69 (dq, J = 10.4, 6.2 1211, 1031, 539.2405 Hz,1H), 4.49 (h, J = 7.4 Hz, 1H), 3.96 734 cm⁻¹ (s, 3H), 3.87 (d, J = 10.3Hz, 1H), 3.77 (s, 3H), 3.74 (s, 3H), 2.16 (s, 3H), 2.10 (s, 3H), 1.23(d, J = 6.1 Hz, 3H), 1.08 (d, J = 7.2 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃)δ 171.12, 165.35, 156.53, 156.28, 152.56, 149.29, 133.74, 133.55,130.86, 130.52, 130.34, 126.82, 126.31, 126.07, 125.57, 123.77, 110.06,109.85, 107.61, 77.23, 73.77, 56.49, 56.25, 55.29, 48.69, 19.22, 17.21,16.33, 16.20. 21 IR (thin HRMS-ESI (m/z) ¹H NMR (400 MHz, CDCl₃) δ 14.15(s, film) 2940, [M + H]⁺ calcd 1H), 12.69 (d, J = 7.0 Hz, 1H), 7.87 (d,J = 1738, 1516, for C₂₅H₂₃F₄N₂O₆, 7.2 Hz, 1H), 7.16-6.91 (m, 6H), 6.781427, 1284, 523.1487; found, (d, J = 7.2 Hz, 1H), 5.63 (dq, J = 9.4, 6.21208, 755, 523.1479 Hz, 1H), 4.53 (p, J = 7.2 Hz, 1H), 4.00 732 cm⁻¹ (d,J = 9.5 Hz, 1H), 3.98 (s, 3H), 1.24 (app t, J = 6.8 Hz, 6H). ¹⁹F NMR(376 MHz, CDCl₃) δ −136.29 (d, J = 21.1 Hz), −136.90 (d, J = 21.1 Hz),−139.33 (d, J = 21.2 Hz), −139.70 (d, J = 21.5 Hz). 22 IR (thin HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.27 (s, film) 2982, [M + H]⁺ calcd1H), 12.61 (d, J = 7.0 Hz, 1H), 7.86 (d, J = 1738, 1571, forC₂₆H₂₈FN₂O₆, 7.2 Hz, 1H), 7.30 (dd, J = 8.7, 5.7 Hz, 1481, 1453,483.1926; found, 1H), 7.26-7.22 (m, 2H), 7.18 (dd, J = 1245, 1157483.1968 8.5, 6.9 Hz, 2H), 7.12-7.06 (m, 1H), cm⁻¹ 6.91-6.81 (m, 2H),6.76 (d, J = 7.2 Hz, 1H), 5.76 (dq, J = 10.3, 6.1 Hz, 1H), 4.52-4.43 (m,1H), 4.29 (d, J = 10.4 Hz, 1H), 3.96 (s, 3H), 2.38 (s, 3H), 1.27 (d, J =6.1 Hz, 3H), 1.05 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ−116.71. 23 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.27 (s,film) 2939, [M + H]⁺ calcd 1H), 12.62 (d, J = 7.0 Hz, 1H), 7.84 (d, J =1737, 1572, for C₂₇H₂₉F₂N₂O₇, 7.1 Hz, 1H), 7.23 (dd, J = 8.5, 6.6 Hz,1502, 1481, 531.1937; found, 1H), 7.10-6.99 (m, 2H), 6.87 (t, J = 9.31208, 734 531.1984 Hz, 1H), 6.75 (d, J = 7.2 Hz, 1H), 6.56 cm⁻¹ (td, J =8.3, 2.5 Hz, 1H), 6.47 (dd, J = 10.9, 2.5 Hz, 1H), 5.74 (dq, J = 10.3,6.1 Hz, 1H), 4.54-4.45 (m, 1H), 4.43 (d, J = 10.3 Hz, 1H), 3.96 (s, 3H),3.77 (s, 3H), 2.21 (d, J = 2.0 Hz, 3H), 1.21 (d, J = 6.1 Hz, 3H), 1.13(d, J = 7.3 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃) δ −113.43, −120.41. 24HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.25 (s, [M + H]⁺ calcd 1H),12.62 (d, J = 7.0 Hz, 1H), 7.84 (d, J = for C₂₆H₂₇F₂N₂O₇, 7.1 Hz, 1H),7.25-7.17 (m, 3H), 6.98- 517.1781; found, 6.90 (m, 2H), 6.75 (d, J = 7.2Hz, 1H), 517.1840 6.55 (td, J = 8.3, 2.5 Hz, 1H), 6.47 (dd, J = 10.9,2.5 Hz, 1H), 5.76 (dq, J = 10.1, 6.2 Hz, 1H), 4.54-4.44 (m, 2H), 3.96(s, 3H), 3.75 (s, 3H), 1.21 (d, J = 6.2 Hz, 3H), 1.14 (d, J = 7.3 Hz,3H). ¹⁹F NMR (471 MHz, CDCl₃) δ −113.26, −116.12. 25 IR (thin HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.31 (s, film) 2981, [M + H]⁺ calcd1H), 12.62 (d, J = 7.0 Hz, 1H), 7.85 (d, J = 1736, 1571, for C₂₇H₃₁N₂O₆,7.2 Hz, 1H), 7.20-7.12 (m, 1H), 7.11- 1479, 1453, 479.2177; found, 7.07(m, 5H), 7.02-6.97 (m, 1H), 1207, 1154, 449.2214 6.94-6.89 (m, 1H), 6.75(d, J = 7.2 Hz, 730 cm⁻¹ 1H), 5.78 (dq, J = 10.4, 6.1 Hz, 1H), 4.53-4.42(m, 1H), 3.98-3.94 (m, 4H), 2.30 (s, 3H), 2.26 (s, 3H), 1.24 (d, J = 6.1Hz, 3H), 1.03 (d, J = 7.2 Hz, 3H). 26 IR (thin HRMS-ESI (m/z) ¹H NMR(500 MHz, CDCl₃) δ 14.28 (s, film) 2935, [M + H]⁺ calcd 1H), 12.61 (d, J= 7.1 Hz, 1H), 7.85 (d, J = 1735, 1510, for C₂₇H₃₁N₂O₈, 7.1 Hz, 1H),7.20-7.11 (m, 4H), 6.83- 1244, 1029, 511.2075; found, 6.68 (m, 5H), 5.70(dq, J = 9.8, 6.1 Hz, 813, 729 511.2128 1H), 4.57-4.38 (m, 1H), 3.96 (s,4H), cm⁻¹ 3.75 (s, 3H), 3.72 (s, 3H), 1.23 (d, J = 6.2 Hz, 3H), 1.11 (d,J = 7.2 Hz, 3H). 27 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ14.29 (s, film) 2984, [M + H]⁺ calcd 1H), 12.71 (d, J = 7.1 Hz, 1H),7.86 (d, J = 1737, 1571, for C₂₆H₂₉N₂O₆, 7.1 Hz, 1H), 7.34-7.08 (m,10H), 1481, 1303, 465.2020; found, 6.75 (d, J = 7.1 Hz, 1H), 5.86 (q, J= 6.2 1223, 1156, 465.2064 Hz, 1H), 4.61-4.52 (m, 1H), 3.96 (s, 702 cm⁻¹3H), 1.74 (s, 3H), 1.21 (d, J = 7.2 Hz, 3H), 1.16 (d, J = 6.3 Hz, 3H).28 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.29 (s, film)2982, [M + H]⁺ calcd 1H), 12.64 (d, J = 7.1 Hz, 1H), 7.86 (d, J = 1737,1634, for C₂₇H₃₀FN₂O₆, 7.1 Hz, 1H), 7.22 (t, J = 7.9 Hz, 1H), 1571,1480, 497.2082; found, 7.16 (d, J = 8.1 Hz, 2H), 7.07 (d, J = 7.8 1453,1209, 497.2118 Hz, 2H), 6.86-6.83 (m, 1H), 6.75 (d, J = 1155, 730 7.2Hz, 1H), 6.74-6.69 (m, 1H), 5.83- cm⁻¹ 5.72 (m, 1H), 4.56-4.48 (m, 1H),4.37 (d, J = 10.3 Hz, 1H), 3.96 (s, 3H), 2.27 (s, 3H), 2.23 (s, 3H),1.25 (d, J = 6.1 Hz, 3H), 1.12 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471 MHz,CDCl₃) δ −119.19. 29 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ14.23 (d, film) 2982, [M + H]⁺ calcd J = 0.5 Hz, 1H), 12.64 (d, J = 6.9Hz, 1738, 1571, for C₂₆H₂₇F₂N₂O₆, 1H), 7.86 (d, J = 7.2 Hz, 1H), 7.26-1481, 1222, 501.1832; found, 7.18 (m, 3H), 6.92-6.82 (m, 4H), 6.77 1158,735 501.1854 (d, J = 7.2 Hz, 1H), 5.70 (dq, J = 9.9, cm⁻¹ 6.1 Hz, 1H),4.54-4.43 (m, 1H), 4.27 (d, J = 10.2 Hz, 1H), 3.97 (s, 3H), 2.35 (s,3H), 1.27 (d, J = 6.2 Hz, 3H), 1.15 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471MHz, CDCl₃) δ −116.00, −116.39. 30 IR (thin HRMS-ESI (m/z) ¹H NMR (500MHz, CDCl₃) δ 14.34 (s, film) 2937, [M + H]⁺ calcd 1H), 12.60 (d, J =7.1 Hz, 1H), 7.84 (d, J = 1736, 1571, for C₂₇H₃₁N₂O₈, 7.2 Hz, 1H), 7.44(dd, J = 7.6, 1.7 Hz, 1491, 1462, 511.2075; found, 1H), 7.26-7.23 (m,1H), 7.15-7.03 1245, 1029, 511.2116 (m, 2H), 6.84-6.80 (m, 3H), 6.74(dd, J = 756 cm⁻¹ 7.9, 1.5 Hz, 2H), 5.95 (dq, J = 10.0, 6.2 Hz, 1H),4.98 (dd, J = 9.8, 2.3 Hz, 1H), 4.57-4.46 (m, 1H), 3.95 (s, 3H), 3.83(s, 3H), 3.74 (s, 3H), 1.24 (d, J = 6.2 Hz, 3H), 1.05 (d, J = 7.3 Hz,3H). 31 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.27 (s,film) 2983, [M + H]⁺ calcd 1H), 12.62 (d, J = 7.0 Hz, 1H), 7.85 (d, J =1737, 1571, for C₂₆H₂₈N₂O₆, 7.2 Hz, 1H), 7.29-7.02 (m, 7H), 6.94- 1503,1453, 483.1926; found, 6.85 (m, 1H), 6.75 (d, J = 7.1 Hz, 1H), 1207,1156 483.1976 5.75 (dq, J = 10.2, 6.2 Hz, 1H), 4.53- cm⁻¹ 4.42 (m, 1H),3.99 (d, J = 10.3 Hz, 1H), 3.96 (s, 3H), 2.22 (d, J = 1.9 Hz, 3H), 1.24(d, J = 6.1 Hz, 3H), 1.03 (d, J = 7.2 Hz, 3H). ¹⁹F NMR (471 MHz, CDCl₃)δ −120.17 32 IR (thin ¹H NMR (500 MHz, CDCl₃) δ 14.31 (s, film) 2981,1H), 12.64 (d, J = 6.9 Hz, 1H), 7.84 (d, J = 1736, 1713, 7.1 Hz, 1H),7.31 (dd, J = 8.6, 6.8 Hz, 1644, 1598, 1H), 7.20-7.12 (m, 1H), 6.75 (d,J = 1571, 1535, 7.2 Hz, 1H), 6.55-6.49 (m, 3H), 6.43 1500, 1426, (dd, J= 11.0, 2.6 Hz, 1H), 5.95-5.88 1221, 1161, (m, 1H), 4.79 (d, J = 10.2Hz, 1H), 4.50 1041, 911, (p, J = 7.1 Hz, 1H), 4.03-3.89 (m, 7H), 735cm⁻¹ 3.85 (dq, J = 9.0, 7.0 Hz, 1H), 1.47 (t, J = 7.0 Hz, 3H), 1.40 (t,J = 6.9 Hz, 3H), 1.23 (d, J = 6.2 Hz, 3H), 1.15 (d, J = 7.3 Hz, 3H). ¹³CNMR (126 MHz, CDCl₃) δ 171.12, 165.38, 157.59, 152.50, 149.29, 148.38,130.82, 107.58, 63.80, 56.51, 48.75, 29.28, 14.62. 33 IR (thin HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.28 (d, film) 2981, [M + H]⁺ calcd J =0.5 Hz, 1H), 12.67 (d, J = 7.1 Hz, 1739, 1644, for C₂₆H₂₈FN₂O₆, 1H),7.86 (d, J = 7.1 Hz, 1H), 7.32- 1571, 1533, 483.1926; found, 7.16 (m,6H), 6.86 (dd, J = 8.2, 1.5 Hz, 1480, 1453, 483.1939 1H), 6.79-6.68 (m,2H), 5.85-5.73 1425, 1302, (m, 1H), 4.53 (p, J = 7.2 Hz, 1H), 4.41 1208,1155, (d, J = 10.2 Hz, 1H), 3.96 (s, 3H), 2.24 1029, 730 (s, 3H), 1.26(d, J = 6.1 Hz, 3H), 1.12 (d, cm⁻¹ J = 7.2 Hz, 3H). ¹³C NMR (126 MHz,CDCl₃) δ 171.01, 165.36, 160.53 (d, J = 245.0 Hz), 152.50, 149.22,140.36, 130.87, 128.74, 128.30, 126.97, 124.80, 123.73, 115.89 (d, J =22.6 Hz), 107.58, 72.81, 56.50, 49.19, 48.55, 29.28, 20.83, 19.11,17.17. 34 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.21 (s,film) 2939, [M + H]⁺ calcd 1H), 12.66 (d, J = 7.0 Hz, 1H), 7.85 (d, J =1736, 1642, for C₂₅H₂₅Cl₂N₂O₆, 7.2 Hz, 1H), 7.28-7.21 (m, 6H), 7.21-1569, 1531, 519.1084; found, 7.13 (m, 2H), 6.76 (d, J = 7.2 Hz, 1H),1479, 1451, 519.1081 5.70 (dq, J = 9.7, 6.2 Hz, 1H), 4.50 (p, J = 1423,1298, 7.2 Hz, 1H), 4.03 (d, J = 9.7 Hz, 1H), 1206, 1153, 3.97 (s, 3H),1.24 (d, J = 6.2 Hz, 3H), 1066, 1013, 1.16 (d, J = 7.2 Hz, 3H). 796, 728¹³C NMR (126 MHz, CDCl₃) δ 170.93, cm⁻¹ 165.42, 152.49, 149.36, 139.34,139.22, 132.99, 132.67, 130.86, 129.40, 129.02, 128.62, 107.64, 72.82,56.52, 56.30, 48.64, 19.00, 17.19. 35 IR (thin HRMS-ESI (m/z) ¹H NMR(500 MHz, CDCl₃) δ 14.21 (d, film) 2982, [M + Na]⁺ calcd J = 0.5 Hz,1H), 12.67 (d, J = 7.1 Hz, 1737, 1643, for C₂₅H₂₄F₂N₂O₆Na, 1H), 7.86 (d,J = 7.1 Hz, 1H), 7.26 (s, 1588, 1532, 509.1495; found, 2H), 7.10-7.04(m, 2H), 6.96 (tt, J = 1481, 1448, 509.1489 9.8, 2.1 Hz, 2H), 6.93-6.89(m, 1H), 1424, 1301, 6.84 (tdd, J = 8.4, 2.6, 0.9 Hz, 1H), 6.76 1205,1149, (d, J = 7.2 Hz, 1H), 5.73 (dq, J = 9.9, 6.2 1028, 950, Hz, 1H),4.51 (p, J = 7.1 Hz, 1H), 4.05 755, 728 (d, J = 9.9 Hz, 1H), 3.97 (s,3H), 1.34- cm⁻¹ 1.22 (m, 3H), 1.14 (d, J = 7.2 Hz, 3H). ¹³C NMR (126MHz, CDCl₃) δ 170.90, 165.38, 162.91 (d, J = 246.9 Hz), 162.73 (d, J =246.3 Hz), 152.50, 149.29, 143.20 (d, J = 7.0 Hz), 142.95 (d, J = 6.8Hz), 130.92, 130.41 (d, J = 8.3 Hz), 130.08 (d, J = 8.5 Hz), 123.69 (d,J = 3.1 Hz), 123.61, 123.40 (d, J = 2.7 Hz), 115.31 (d, J = 20.7 Hz),114.16 (d, J = 20.9 Hz), 113.81 (d, J = 20.9 Hz), 107.62, 72.88, 57.06,56.53, 48.55, 29.28, 19.03, 17.19. 36 IR (thin HRMS-ESI (m/z) ¹H NMR(500 MHz, CDCl₃) δ 14.28 (s, film) 2939, [M + Na]⁺ calcd 1H), 12.63 (d,J = 7.1 Hz, 1H), 7.85 (d, J = 2835, 1736, for C₂₇H₃₀N₂O₈Na, 7.2 Hz, 1H),7.20 (t, J = 8.0 Hz, 1H), 1643, 1596, 533.1894; found, 7.13 (t, J = 8.0Hz, 1H), 6.89 (ddt, J = 1570, 1531, 533.1888 7.7, 2.8, 1.2 Hz, 2H), 6.82(t, J = 2.1 Hz, 1482, 1451, 2H), 6.78-6.69 (m, 2H), 6.65 (ddd, J = 1424,1296, 8.2, 2.6, 0.9 Hz, 1H), 5.78 (dq, J = 10.5, 1206, 1151, 6.1 Hz,1H), 4.49 (p, J = 7.2 Hz, 1H), 1029, 755, 4.02-3.94 (m, 4H), 3.77 (s,3H), 3.74 728 cm⁻¹ (s, 3H), 1.26 (d, J = 6.1 Hz, 3H), 1.08 (d, J = 7.2Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.02, 165.32, 159.75, 159.56,152.52, 149.24, 142.89, 142.61, 130.85, 129.77, 129.40, 123.73, 120.38,120.08, 114.30, 113.93, 111.85, 107.56, 73.24, 57.91, 56.51, 55.12,48.60, 19.17, 17.15. 37 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃)δ 14.28 (s, film) 2939, [M + H]⁺ calcd 1H), 12.64 (d, J = 7.0 Hz, 1H),7.84 (d, J = 1735, 1643, for C₂₇H₂₉Cl₂N₂O₈, 7.2 Hz, 1H), 7.31 (d, J =8.3 Hz, 1H), 1591, 1572, 579.1295; found, 7.09 (d, J = 8.2 Hz, 1H),6.84-6.78 (m, 1487, 1452, 579.1298 3H), 6.75 (d, J = 7.2 Hz, 1H), 6.72(d, J = 1301, 1245, 2.0 Hz, 1H), 5.87 (dq, J = 9.6, 6.1 Hz, 1209, 1150,1H), 4.81 (d, J = 9.7 Hz, 1H), 4.51 (p, J = 1027, 727 7.2 Hz, 1H), 3.96(s, 3H), 3.82 (s, 3H), cm⁻¹ 3.73 (s, 3H), 1.22 (d, J = 6.2 Hz, 3H), 1.16(d, J = 7.2 Hz, 3H). ¹³C NMR (126 MHz, CDCl₃) δ 171.03, 165.37, 157.98,157.84, 152.49, 149.30, 133.15, 132.79, 130.83, 130.43, 129.91, 127.51(d, J = 3.3 Hz), 123.66, 120.41, 120.02, 111.62, 111.35, 107.60, 72.33,56.49, 55.70 (d, J = 6.9 Hz), 48.69, 18.75, 17.29. 38 IR (thin HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.22 (d, film) 2982, [M + H]⁺ calcd J =0.5 Hz, 1H), 12.66 (d, J = 7.1 Hz, 1736, 1643, for C₂₆H₂₇F₂N₂O₆, 1H),7.84 (d, J = 7.2 Hz, 1H), 7.30 (dd, J = 1569, 1532, 501.1832; found,8.7, 5.8 Hz, 1H), 7.21-7.12 (m, 3H), 1508, 1479, 501.1847 6.96 (t, J =8.6 Hz, 1H), 6.86 (td, J = 1423, 1218, 8.5, 3.0 Hz, 1H), 6.76 (d, J =7.2 Hz, 1178, 1154, 1H), 6.72 (dd, J = 9.7, 2.8 Hz, 1H), 5.67 805, 727(dq, J = 10.0, 6.1 Hz, 1H), 4.49 (p, J = cm⁻¹ 7.2 Hz, 1H), 4.24 (d, J =10.0 Hz, 1H), 3.97 (s, 3H), 2.27 (s, 3H), 1.24 (d, J = 6.1 Hz, 3H), 1.14(d, J = 7.2 Hz, 3H). 39 IR (thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃)δ 14.30 (s, film) 2980, [M + Na]⁺ calcd 1H), 12.63 (d, J = 7.1 Hz, 1H),7.85 (d, J = 2937, 1735, for C₂₇H₃₀N₂O₆Na, 7.2 Hz, 1H), 7.18-7.13 (m,4H), 7.06 1642, 1568, 501.1996; found, (d, J = 7.8 Hz, 2H), 6.99 (d, J =7.8 Hz, 1478, 1450, 501.1987 2H), 6.75 (d, J = 7.2 Hz, 1H), 5.76 (dq, J= 1422, 1298, 10.2, 6.1 Hz, 1H), 4.49 (p, J = 7.3 Hz, 1206, 1153, 1H),3.98 (d, J = 7.6 Hz, 1H), 3.96 (s, 1028, 804, 3H), 2.27 (s, 3H), 2.23(s, 3H), 1.24 (d, J = 756, 726 6.1 Hz, 3H), 1.07 (d, J = 7.2 Hz, 3H).cm⁻¹ ¹³C NMR (126 MHz, CDCl₃) δ 171.02, 165.31, 152.50, 149.22, 138.69,138.53, 136.34, 135.99, 130.84, 129.40, 129.02, 127.90, 127.77, 123.77,107.56, 73.53, 57.04, 56.49, 48.60, 20.96, 20.90, 19.18, 17.15. 40 IR(thin HRMS-ESI (m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.35 film) 2939, [M +Na]⁺ calcd (s, 1H), 12.63 (d, J = 6.1 Hz, 1H), 7.86- 1735, 1644, forC₂₉H₃₄N₂O₁₀Na, 7.79 (m, 1H), 7.06 (dt, J = 8.4, 1.6 1571, 1535,593.2106; found, Hz, 1H), 7.03-6.97 (m, 1H), 6.91- 1474, 1425, 593.21006.80 (m, 1H), 6.80-6.68 (m, 4H), 5.74- 1274, 1218, 5.61 (m, 1H),5.16-5.03 (m, 1H), 1154, 1066, 4.56-4.38 (m, 1H), 3.96 (s, 3H), 3.891046, 1003, (s, 3H), 3.83 (s, 3H), 3.79 (s, 3H), 3.71 726 cm⁻¹ (s, 3H),1.36 (d, J = 7.2 Hz, 3H), 1.11 (d, J = 7.3 Hz, 3H). 41 IR (thin HRMS-ESI(m/z) ¹H NMR (500 MHz, CDCl₃) δ 14.28 (d, film) 2940, [M + Na]⁺ calcd J= 0.5 Hz, 1H), 12.66 (d, J = 7.0 Hz, 1736, 1643, for C₂₇H₂₈F₂N₂O₈Na,1H), 7.85 (d, J = 7.1 Hz, 1H), 7.18 (ddd, 1570, 1533, 569.1706; found, J= 17.3, 9.7, 3.1 Hz, 1H), 6.97-6.91 1493, 1454, 569.1700 (m, 1H),6.89-6.72 (m, 4H), 6.70 (dt, J = 1423, 1243, 9.0, 4.6 Hz, 1H), 5.93-5.79(m, 1H), 1205, 1178, 4.85 (d, J = 9.5 Hz, 1H), 4.56-4.43 (m, 1152, 1026,1H), 3.97 (s, 3H), 3.82 (s, 3H), 3.73 (s, 808, 726 3H), 1.30-1.22 (m,3H), 1.17 (d, J = cm⁻¹ 7.2 Hz, 3H).

TABLE 3 Biological Testing Rating Scale Rating Table for FungalPathogens % Control Rating >80 A ≦80 B Not Tested C No Activity Observedin D the Reported Assay

TABLE 4 Biological Activity - PUCCRT and SEPTTR Disease Control in Highand Low Volume Applications HV activity at 100 ppm LV activity at 121.5g/H PUCCRT* SEPTTR* PUCCRT* SEPTTR* Cmpd. No. 1DP* 3DC* 1DP* 3DC* 1DP*3DC* 1DP* 3DC* 1 A B A A A B A A 2 A A A A A A A D 3 A A A B A B A B 4 AB B D D D D A 5 D D A B B D A B 6 A D A A B D A A 7 C C C C A B A A 8 CC C C B A D B 9 D D A D D D A D 10 A A B D A A A D 11 D D A D D D A B 12A B A A A B A A 13 A A A A A B A A 14 C C C C C C C C 15 C C C C B B A A16 C C C C C C C C 17 C C C C B B A A 18 C C C C B B A A 19 C C C C B BA A 20 C C C C C C C C 21 C C C C D B A A 22 A A A A A A A A 23 A A A AC C C C 24 A A A A A B A A 25 A A A A A A A A 26 A A A A C C C C 27 D DA A D D B B 28 A D A A A B A A 29 A A A A A B A A 30 C C C C B B A A 31A A A A A B A A 32 C C C C B D B B 33 C C C C B D A B 34 C C C C A D A A35 C C C C D D B B 36 C C C C B D B D 37 C C C C A D A B 38 C C C C B DA A 39 C C C C B D A B 40 C C C C D D D B 41 C C C C D D B B *Cmpd.No.—Compound Number *PUCCRT—Wheat Brown Rust (Puccinia triticina)*SEPTTR—Wheat Leaf Blotch (Zymoseptoria tritici) *1DP—1 Day Protectant*3DC—3 Day Curative *g/H—Grams Per Hectare *ppm—Parts Per Million

TABLE 5 Biological Activity - Disease Control at 25 ppm PHAKPA* Cmpd.No. 1DP* 3DC* 1 A D 2 B D 3 D D 4 B D 5 D D 6 D D 7 D B 8 B D 9 D D 10 AB 11 D D 12 B B *Cmpd. No.—Compound Number *PHAKPA—Asian Soybean Rust(Phakopsora pachyrhizi) *1DP—1 Day Protectant *3DC—3 Day Curative

What is claimed is:
 1. A composition for the control of a fungalpathogen including mixtures of at least one the compounds of Formula I,

wherein: R₁ is hydrogen or C₁-C₅ alkyl, each optionally substituted with0, 1 or multiple R₆; R₂ is hydrogen, C₁-C₅ alkyl or cycloalkyl, eachoptionally substituted with 0, 1 or multiple R₆; R₃ is alkyl,cycloalkyl, aryl or heteroaryl, each optionally substituted with 0, 1 ormultiple R₆; R₄ is hydrogen, halo, hydroxyl, alkyl, or alkoxy; R₅ isalkyl, cycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy,each optionally substituted with 0, 1 or multiple R₆; R₆ is hydrogen,alkyl, aryl, acyl, halo, alkoxy, or heterocyclyl, each optionallysubstituted with 0, 1 or multiple R₇; R₇ is hydrogen, alkyl, aryl, acyl,halo, alkoxy, or heterocyclyl; R₈ is hydrogen or C₁-C₅ alkyl, eachoptionally substituted with 0, 1 or multiple R₆. and a phytologicallyacceptable carrier material.
 2. The composition according to claim 1,wherein R₁ and R₈ are independently hydrogen or C₁-C₅ alkyl.
 3. Thecomposition according to claim 2, wherein R₂ is C₁-C₅ alkyl.
 4. Thecomposition according to claim 2, wherein R₃ and R₅ are independentlyaryl, each optionally substituted with 0, 1, or multiple R₆.
 5. Thecomposition according to claim 2, wherein R₄ is hydrogen.
 6. Thecomposition according to claim 2, wherein R₁ and R₈ are independentlyhydrogen or C₁-C₅ alkyl, R₂ is C₁-C₅ alkyl, R₃ and R₅ are independentlyaryl, each optionally substituted with 0, 1, or multiple R_(6,) and R₄is hydrogen.
 7. The composition according to claim 1 wherein the fungalpathogen is one of Leaf Blotch of Wheat (Zymoseptoria tritici), WheatBrown Rust (Puccinia triticina), Stripe Rust (Puccinia striiformis),Scab of Apple (Venturia inaequalis), Blister Smut of Maize (Ustilagomaydis), Powdery Mildew of Grapevine (Uncinula necator), Barley scald(Rhynchosporium secalis), Blast of Rice (Pyricularia oryzae), Rust ofSoybean (Phakopsora pachyrhizi), Glume Blotch of Wheat (Leptosphaerianodorum), Powdery Mildew of Wheat (Blumeria graminis f. sp. tritici),Powdery Mildew of Barley (Blumeria graminis f. sp. hordei), PowderyMildew of Cucurbits (Erysiphe cichoracearum), Anthracnose of Cucurbits(Colletotrichum lagenarium), Leaf Spot of Beet (Cercospora beticola),Early Blight of Tomato (Alternaria solani), and Net Blotch of Barley(Pyrenophora teres).
 8. The compostion according to claim 6 wherein thefungal pathogen is one of Leaf Blotch of Wheat (Zymoseptoria tritici),Wheat Brown Rust (Puccinia triticina), Scab of Apple (Venturiainaequalis), Barley scald (Rhynchosporium secalis), Blast of Rice(Pyricularia oryzae), Rust of Soybean (Phakopsora pachyrhizi), GlumeBlotch of Wheat (Leptosphaeria nodorum), Anthracnose of Cucurbits(Colletotrichum lagenarium), Leaf Spot of Beet (Cercospora beticola),and Early Blight of Tomato (Alternaria solani).
 9. A method for thecontrol and prevention of fungal attack on a plant, the method includingthe step of: applying a fungicidally effective amount of at least one ofthe compositions of claim 6 to at least one of the plant, an areaadjacent to the plant, soil adapted to support growth of the plant, aroot of the plant, and foliage of the plant.